It is well known that regulating the exposure of oxygen-sensitive products to oxygen maintains and enhances the quality and "shelf-life" of the product. For instance, by limiting the oxygen exposure of oxygen sensitive food products in a packaging system, the quality of the food product is maintained, and food spoilage is avoided. In addition such packaging also keeps the product in inventory longer, thereby reducing costs incurred from waste and having to restock inventory. In the food packaging industry, several means for regulating oxygen exposure have already been developed. These means include modified atmosphere packaging (MAP) and oxygen barrier film packaging.
One method currently being used is through "active packaging," whereby the package for the food product is modified in some manner to regulate the food product's exposure to oxygen. See Labuza and Breene, "Application of `Active Packaging` for Improvement of Shelf Life and Nutritional Quality of Fresh and Extended Shelf-Life Foods," Journal of Food Processing and Preservation, Vol. 13, pp. 1-69 (1989). The inclusion of oxygen scavengers within the cavity of the package ("headspace") is one form of active packaging. Typically, such oxygen scavengers are in the form of sachets which contain a composition which scavenges the oxygen through oxidation reactions. One sachet contains iron-based compositions which oxidize to their ferric states. Another type of sachet contains unsaturated fatty acid salts on a particulate adsorbent, see U.S. Pat. No. 4,908,151, or a low molecular weight hydrocarbon mixture or a low molecular weight hydrocarbon with a fatty acid salt and optimally, a humidity adjusting agent, see European Patent Application 454,437 A1. Yet another sachet contains metal/polyamide complex. See PCT Application 90/00578.
However, one disadvantage of sachets is the need for additional packaging operations to add the sachet to each package. A further disadvantage arising from the iron-based sachets is that certain atmospheric conditions (e.g., high humidity, low CO.sub.2 level) in the package are sometimes required in order for scavenging to occur at an adequate rate.
Another means for regulating the exposure to oxygen involves incorporating an oxygen scavenger into the packaging structure itself. Through the incorporation of the scavenging material in the package itself rather than by addition of a separate scavenger structure (e.g., a sachet) to the package, a more uniform scavenging effect throughout the package is achieved. This may be especially important where there is restricted air flow inside the package. In addition, such incorporation can provide a means of intercepting and scavenging oxygen as it is passing through the walls of the package (herein referred to as an "active oxygen barrier"), thereby maintaining the lowest possible oxygen level throughout the package.
One attempt to prepare an oxygen-scavenging wall involves the incorporation of inorganic powders and/or salts. See European Applications 367,835; 366,254; 367,390; and 370,802. However, incorporation of these powders and/or salts causes degradation of the wall's transparency and mechanical properties such as tear strength. In addition, these compounds can lead to processing difficulties, especially in the fabrication of thin layers such as thin films. Even further, the scavenging rates for walls containing these compounds appear to be unsuitable for many commercial oxygen-scavenging applications, e.g. such as those in which sachets are employed.
The oxygen scavenging systems disclosed in U.S. Pat. Nos. 5,021,515 issued to Cochran et al. Jun. 4, 1991 and 5,049,624 issued to Adams et al. Sep. 17, 1991 illustrate another attempt to produce an oxygen-scavenging wall. These patent applications disclose incorporating a metal catalyst-polyamide oxygen scavenging system into the package wall. The rate of oxygen scavenging, however, is too low for the inventors' purpose.
European Application 301,719 (Example 7) illustrates that adding these materials to a high-barrier package containing air produces a package which is not generally suitable for creating an internal oxygen level of less than 0.1% (starting with air) within a period of four weeks or less at room temperature, as is typically required for headspace oxygen scavenging applications. See Mitsubishi Gas Chemical Company, Inc.'s literature titled "AGELESS.RTM.-A New Age in Food Preservation" (date unknown).
Further, in regards to the incorporation of the polyamide/catalyst system into the package wall, polyamides are typically incompatible with the thermoplastic polymers, e.g. ethylene-vinyl acetate copolymers and low density polyethylenes, typically used to make flexible package walls. Even further, certain polyamides, which are suitable for rigid structures such as bottles, can make inappropriately stiff structures, when incorporated into flexible packaging walls. Polyamides also incur processing difficulties and higher costs when compared with the costs of thermoplastic polymers typically used to make flexible packaging. Even further, they are sometimes difficult to heat seal. Thus, all of these are factors to consider when selecting materials for packages, especially flexible packages and when selecting systems for reducing oxygen exposure of packaged products.
The oxygen scavengers of the present invention are disclosed in copending U.S. Ser. No. 679,419 filed Apr. 2, 1991, and a method of initiating oxygen scavenging generally is disclosed in U.S. Pat. No. 5,211,875 issued May 18, 1993. Both applications are incorporated herein by reference as if set forth in full. It has been found that these oxygen scavengers have a demonstrable effect on the shelf stability of certain food products. Further, these materials can be used as a lidstock or incorporated in multilayer packaging materials to produce thin, flexible, transparent films having an oxygen transmission of less than about 1 cc O.sub.2 /(m.sup.2 .multidot.atm.multidot.day), more preferably less than 0.5, and even more preferably, less than 0.05 cc O.sub.2 /(m.sup.2 .multidot.atm.multidot.day). These films are an effective substitute for a 15-40 micrometer layer of aluminum foil in some applications.
It has also been found that these materials have special use in certain applications, where the oxygen scavenger can be used to compensate for another oxygen barrier material's sensitivity to humidity or heat.
Finally, the oxygen scavenging materials are both permeable to other gases and selective. They can be incorporated into generally gas permeable packaging for the purpose of producing an enhanced oxygen barrier while substantially maintaining the overall transmission rates of other gases such as carbon dioxide. Such packaging is especially useful where a product is sensitive to oxygen and also gives off another gas.